Condensation products of the naphthoquinone-imine series



Patented May 15, 1951 UNITED STATES PATENT OFFICE CONDENSATION PRODUCTS OF THE NAPHTHOQUINONE-IMINE SERIES Valentin Kartaschofi and Ernest Merian, Basel, Switzerland, assignors to Sandoz, A, G., Basel, Switzerland, a Swiss firm N Drawing. Application February 13, 1950, Se-

rial No. 144,041. In Switzerland February 24,

14 Claims.

This invention relates to the preparation of new and valuable compounds of the naphthoquinone-imine series.

It is known that if dinitronaphthalene is reduced in sulfuric acid a compound generally re ferred to as naphthazarine intermediate having the formula ItH H or-according to the modern writing is produced, and that this compound can be condensed with amines and further sulfonated to yield dyestuffs.

It has been found that while the condensation products obtained by condensing the naphthazarine intermediate with amines, are more fully described in U. S. Patent No. 647,370, and having the general formula -X being -H, CH3 or NH2, are suitable for coloring oils, fats and waxes, including petroleum oil fractions such as gasoline in beautiful green shades, and if sulfonated are useful as acid wool dyestuffs, they have practically no affinity for cellulose acetate and superpolyamides.

It has further been ascertained that while the condensation products obtained by condensing the naphthazarine intermediate with only one amine, as more fully described in U. S, Patents 2 Nos. 2,066,119 and 2,135,366 and having the general formula -X being -H, -OH, --NH2, O-alkyl or O- alkyl 'OI-I are suitable for dyeing cellulose acetate and superpolyamides, the results are only blue to greenish-blue shades.

It is an object of this invention to produce a new class of condensation products, by condensing one mole of naphthazarine intermediate with one mole of an aromatic aminoazo compound, which are suitable for dyeing cellulose acetate and superpolyamides in beautiful green, yellowish-green, olive and brown shades. T

It could not be expected that aminoazo compounds can easily be condensed with naphthazarine intermediate as this derivative can only be condensed with a small selection of aromatic amines. It is furthermore very surprising that these new condensation products have such a great affinity for cellulose acetate and superpo1y-- amides, since for instance the condensation products of the formulae and have practically no afinity for cellulose acetate and superpolyamides.

It is a further object of this invention to dye 'cellulose ester fibers, synthetic polyamide fibers and polyurethane fibers in green, yellowishgreen, olive and brown shades with uniform dye stuffs of the dispersed type. Up to now these shades were produced either by using dyestuff mixtures of the dispersed type, i. e. mixture of yellow and blue dyestuffs, or by dyeing cellulose acetate and superpolyamides with aromatic aminoazo compounds followed by diazotizing and developing with suitable coupling compounds, this process being very complicated. Dyestuff mixtures of the dispersed types moreover, have the disadvantage that, depending upon the method of dyeing, different-shades are Obtained, being sometimes more yellow, and sometimes more blue. Furthermore, these mixtures are either fast to light or fast to gas-fumes, according to the blue component employed.

It is therefore a further object of this invention to, dye cellulose ester fibers, synthetic polyamide fibers and polyurethane fibers in green, yellowish green, olive and brown shades of good fastness to light and to gas-fumes, with uniform dyestuffs of the dispersed type which can be discharged in light shades. giving a pure White.

As aminoazo compounds suitable for condensation. With the naphthazarine intermediate, the most varied substituted derivatives of the general formula wherein X, Y and Z stand for hydrogen or a-substituent other than the sulfom'cacid group and wherein R is a carbocyclic or a heterocyclic radical, can be used, as for example 4-aminoazobenzene, l-aminoazotoluene, 4 amino-l-nitroazobenzene, 4-amino-4 carboxyazobenzene, 4- amino-4-dimethylaminoazobenzene, 4-amino-4 ethyl hydroxyethylaminoazob'enzene, 4-amino- 4 hydroxyethylaminoazobenzene, 4' amino-4- ethylglycerylaminoazobenzene, -aminobenzeneazonaphthalene, 4-amino-2-hydroxyazobenzene, 4-ethoxy-4 amino Z-hydroxyazobenzene, aniline-(4'-azo-4) (B-methylpyrazolone (5)), 4- amino 2' hydr0xy-5 methylazobenzene and so on.

In so far as these compounds have not been previously described, they can be obtained by coupling dia'zotized nitro'anilines, with the desired coupling components and subsequent reduction of the nitro group with e. g. sodium sulphide or sodium sulfhydrate or by coupling diazotized aminoacetanilides or any other amino acylanilides followed by a hydrolysis of the acylamido-group.

The condensation with the naphthoquinoneimine is advantageously carried out in the presence of a solvent which is indifferent to the reaction compounds, such as e. g. acetic acid, propionic acid, ethanol, isopropanol, and dilute acetic acid, at an elevated'temperature and may also advantageously be carried out in presence of a condensation accelerator such as boric acid, copper, copper salts, sodium acetate and the like.

The new condensation products thu obtained correspond to the general formula in which X, Y and Z are hydrogenor a substituent other than the sulfonic acidv group and R is a carbocyclic or a heterocyclic radical.

These new compounds dissolve in organic s01- vents with green, yellowish-green, olive or brown colors. They can be'used either as dyestuffs for cellulose ester fibers, synthetic polyamide and polyurethane fibers or as intermediates for the preparation of other dyestuffs.

The following examples illustrate how the invention may be carried out in practice, but the examples are in no waylim'itative. Parts are by weight and temperatures in degrees centigrade.

Example 1 40 parts of 5-am'ino-8-hydroxy-1.4-naphthoquinone-imine-(l), i. e. of naphthazarine intermediate, are dissolved in 400 parts of boiling glacial acetic acid. The mass is then cooled to and at this temperature 40 parts of 4-aminoazobenzene are added. The condensation is finished after about 2 hours and the solution is then dark green. The melt is then poured into 1500 parts of ice water, filtered and Washed free from a small excess of aminoazobenzene with warm water. The residue dissolves in ethanol with a green color and in concentrated sulfuric acid; with a greenish-yellow color which becomes green on the addition of paraformaldehyde. It, corresponds to the formula and dyes acetate silk and nylon in suspension a pure green shade.. Similar products are obtained by using ethanol, isopropanol, dilute acetic acid or propionic acid in lieu of the glacial acetic acid.

Example 2 If the aminoazobenzene in Example 1 is replaced by 45- parts' of 4-aminoazotoluene,there is obtaineda similar 'procbuct which is more yellowish when dyed on acetate silk and nylon and which corresponds to the formula CH3 CH3 Example 3 30 parts of 5-amino-8-hydroxy-1.4-naphthoquinone-imine-(l) are stirred with 300 parts of glacial acetic acid for half an hour at 110. Thereupon it is cooled to 80 and 44 parts of 4- amino 4 ethylhydroxyethyl-aminoazobenzene added, and stirred for a further hour. pourin into water a black-green powder is obtained which dissolves in alcohol with a yellowish orange color and in concentrated sulfuric acid with a yellow color which after addition of paraformaldehyde becomes yellowish-green. It corresponds to the formula H and dyes acetate silk yellowish-brown and nylon 6 a test specimen dissolves in ethanol with a brown color. The reaction mass is poured into water, filtered, washed and dried. The dark-brown powder dyes acetate silk yellowish and nylon reddish brown.

Example 5 46.5 parts of raw material containing 81% of naphthazarine intermediate, as it is obtained from 1.5-dinitronaphthalene, are stirred up in 450 parts of acetic acid at 80 in presence of 45.5 parts of 4-amino-2'-hydroxy-5'-methyl-azobenzene. After 3 hours the reaction mass is heated for 1 hour up to 90, when it is poured into iceand dyes acetate silk and nylon very strong yellowish olive shades.

A series of similar condensation products is made by proceeding in accordance with the foregoing examples, the properties of which are listed, in the following table: 7

Color of the sol.

Color of the solu- Color of the sol.

in cone. sulfuric Color of dyeing Amino compound used for the Color of dyeing on condensation tion in ethanol g a-g summc ZF gfigffigig: acetate silk on nylon hyde 4-aminoazobenzene green.. yellow-green green pure green. pure green. 7 v 4-aminoazotolene yellowish green... yellow brown. yellowish green... yellowish green; 4-amino-4-nitro-azobenzene brown ..do orange.- yellowish brown... reddish brown. 4'-amino-4-dimethylamino-azobenzene.-. greenish blue greenish blue blue-green. green-blue green-blue. 4-amino-4-ethyl-glycerylarnino-azobengrass-green yellow-green yellow-olive blu1sh-green bluish-green.

zene. 4-emino-4-hydroxyethylamino-azobenblue-green greenish-yellow.... olive-green greenish-'blue.....'. greenish-blue xene. v 4- amino -4- ethyl -hydroxyethylami11oyelloW-orange.--.. yellow yellow-green yellowish-brown. brownish-oliye azobenzene. 4-amino-4-carboXy-azobenzene 4- ammo 2 hydroxy 5 methyl azobenzene.

yellowish green grass-green greenish brown brown green reddish brown.

green. yellowish olive...

4-amino-Z-hydroxy-azobenzene yellowish greenw. yellowish brown. red-brown yellow'-green-...;. yellow-green;

41-h ethcxy 4 amino 2 hydroxy azo- ..--.do carmme olive-brown do... yellowish olive.

enzene.

4-aminobenzene-azonapthalene-(l) bluish green blue-green blue-violet blue bluish greenr Arlliline azo 4)-(3 methyl pyrezoblue-green yellow-green green greenish blue blue-green. one-(5 4-benzeneazo-naphthylaminel) green olive brown olive olive-brown. I

4- amino 4 dihydroxyethy aminoyellow-orange yellow-green.

yellowish brown.

brownish olive.

azobenzene.

brownish olive. It corresponds to the formula Example 4 While the dye compounds of the invention have been described more particularly in con.- nection with the coloration of cellulose acetate and nylon textile materials, it is to be noted that they are useful for the coloration of the other materials named herein and that they yield about the same colors on these materials as they do on cellulose acetate and nylon.

These dyes may be advantageously directly applied to the material undergoing coloration in the form of an aqueous suspension which can be prepared by milling the dye together with a suitable dispersing agent, such as e. g. the condensation product of beta-naphthalene-sulfonic acid and formaldehyde, a sulfonated aliphatic alcohol or soap, in presence of common salt, sodium sulfate i. e. to get more eflicient milling, and bygrindin'g-said mixture to 'a paste inthe presence of "a 'sulfonate'd oil, soap or other suitable. dispersing he QQQQHCQEQ t mperatures aheut 60-85.

but a y u ta e t m eratu may be used. Thus,

the tex i e mat r a to b tire o co ored is ordieerily d e to t e dr h th t. a temp a u e lewerth n t a at which the mai or f the d e n s o be c ed. a m r e pprox mating 45-55% for example, following which the temp r ure is r i ed t tha s l cted f ee ryin but he yei ope t on The ra e atwhich the dyeing is conducted may of course be varied somewhat depending upon the particular material undergoing coloration. As is understood by those skilled in the art, the intensity of dyeing can be varied by varying the proportion of dye to material undergoing coloration. Generally speaking 0.14% by weight of dye to material is employed although any desired-proportions can be used.

The following example is given to illustrate a method for applying such colors to cellulose acetate fibers:

Example 6 40' parts of the insoluble dye of Example 1 are milled together with 40 parts of; the sodium salt of a fatty alcohol sulfonate and 20' parts of; sodium sulfate. The powder thus obtained is mixed first with the same weight of a highly sulfonated Turkey red oil into a fine paste, upon which water at 60 is poured. The whole is stirred until uniform dispersion is obtained, when it is added to the dye-bath througha sieve. The volume of dye liquor is 1:20 on the Weight of the material, the dye-bath being made up with the requisite amount of color and 2 grams of fatty alcohol sulfonate perliter. The material is entered at 40-60% the temperature is slowly raised to 80 and dyeing is c ntinuedat. this tempera re fo 1 hour- Afte dyeing, the goods are well washed off. One ob.- tains pure green shades fast to light, to gas-fumes andto washing.

Th pro ss. as .pr c din ly disclosed. for the dyeing of cellulose acetate, can be used in applying the dyes'of the present invention to other cellulose ester fibers, to synthetic polyamide fibers andto polyurethane fibers.

Having thus disclosed theinvention, what is claimed is:

"l. A process for the manufacture of a condensation product of the naphthoquinone-imine serie co ising the step Q c nde in -arnino- 8-hydroxy-1- p t oqui 0n nnin (1) in. a solvent w th an quimeleeular quan ity of a aremati' amin azo om o n f ee rom s lfhnie acid groups, at a temp rature f at l a 6 C;

A, process for the manufacture Q a con- .densati n product f the n ph hq ui onem he series, comprising thestep of condensing '5-am ino- 8-hydroxy-Lsrnaphthequihon dmine-(l2 in a solvent th an equirnole lar. uantity .ofa ar matie amiheazo commend which eerres e ds. o the formula in which: 1. 21 s and f r s member selected 8 from the group'consisting of hydrogen, lower alkyl, hydroxy, nitro, alkylamino, dialkylamino, alkoxy, hydroxyalkylamino, dihydroxydialkylamino, alkylhydroxyalkylamino and carboxy at a temperature of at least C.

3. A process for the manufacture of a condensation product of the naphthoquinone-imine series, comprising the step of condensing 5-amino- 8-hydroxy-1.4-naphthoquinone-imine-(l) in a solvent with -aminoazobenzene at a temperature of at least 60 C.

4. A process for the manufacture of a condensation product of; the naphthoquinone-imine s ries. comp is g t e ep o nd ns n -amin 8-hydroxy-1.4-naphthoquinone-imineefl) in a solvent with 4eamino-l-nitro=azobenzene at a temperature of at least 60 C.

5. A process for the manufacture of a con.- densatidn product of the naphthoquinoneeimine series. comprising the step of condensing 5-,amino.- 8-hydroxy-l.sl-naphthoquinone-imine-(1) in a solvent with 4 samino-.4-ethyl-hydroxyethyle amino-azobenzene at a temperature of at least 60 C.

6. The condensation products of the naphthoe quinone-lmine series, corresponding to the general formula wherein X, Y and Z stand for a member selected from the group consisting of hydrogen, lower alkyl, hydroxy, nitro, alkylamino, dialkylamino, alkoxy, hydroxyalkyl-amino, .dihydroxydialkylamino, alkylhydroxyalkylamino and carboxy.

8. The condensation product of the. naphthoquinone-imine series of the formula 9 10 9. The condensation product of the naphtho- 12. The condensation product of the naphthaquinone-imine series of the formula quinone-imine series of the formula N O N O O N N: Q a

N NH

H 10. The condensation product of the naphthoquinonedmine Series of the formula 13. A process for the manufacture of a con- 0 H densation product of the naphthoquinone-imine 2 5 series, comprising the step of condensing 5-aminoo NC -N=NON 8-hydroxy-Le-naphthoquinone-imine-(1) in a.

\CZHPMI solvent with 4-amino-azoto1uene at a temperature of at least 60 C.

14. A process for the manufacture of a condensation product of the naphthoquinone-imine series, comprising the step of condensing S-amino- NH 8-hydr0xy-1.-naphthoquinone-imine-(1) in a solvent with 4-amino-2'-hydroxy-5'-methy1azonzn tre fa1ast60 i1. The condensation firoduct (if the naphthobe e e at gg f i g KZRTASCIEOFE quinone-imme series of t e formu a ERNEST MERIAN H (EH3 CH3 No references cited. 

8. THE CONDENSATION PRODUCT OF THE NAPHTHOQUINONE-IMINE SERIES OF THE FORMULA 